CN103476802B - Modified cellulose nanofiber, its production method and use its resin combination - Google Patents

Modified cellulose nanofiber, its production method and use its resin combination Download PDF

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CN103476802B
CN103476802B CN201280018083.6A CN201280018083A CN103476802B CN 103476802 B CN103476802 B CN 103476802B CN 201280018083 A CN201280018083 A CN 201280018083A CN 103476802 B CN103476802 B CN 103476802B
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resin
acid
anionic property
fibrous
cellulose
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CN103476802A (en
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原田哲哉
片野聪
佐藤明弘
宫本和也
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Nippon Pmc K K
DIC Corp
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Nippon Pmc K K
Dainippon Ink and Chemicals Co Ltd
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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Abstract

The present invention relates to modified cellulose nanofiber, it is characterised in that use anionic property additive to neutralize the cation group that cationic is cellulose nano-fibrous.The invention still further relates to: comprise the resin combination of aforementioned modified cellulose nano-fibrous and moulding resin；With the formed body by being molded the acquisition of described resin combination.The invention further relates to manufacture modified cellulose nano-fibrous method, described method is characterised by using anionic property additive to neutralize the cation group that cationic is cellulose nano-fibrous.

Description

Modified cellulose nanofiber, its production method and use its resin combination
Technical field
The present invention relates to by modified fine with what anionic property additive obtained with cationic cellulose Dimension element nanofiber, its production method, the resin combination comprising modified cellulose nanofiber and one-tenth thereof Type body.
Background technology
Comprise string such as hemp, cotton, jute, wood pulp or the bamboo etc. of cellulose such as paper, clothing The various application such as clothes and packaging material have been used as the renewable raw materials of natural origin.Cellulose is polysaccharide Class, it does not the most exist with molecular forms, but uses with by the fibre formed that gathers materials of cellulosic molecule Tie up plain micro-fibril, many by the form of the gather materials micro-fibril bundle formed and the aggregation thereof of the micro-fibril of cellulose Rotating fields.
In recent years, have been developed for by making to comprise planting of cellulose by means of mechanically and/or chemically processing Fibres solution fine (fibrillating) obtains cellulose nano-fibrous technology, and these to nanometer level Cellulose nano-fibrous as the resin composite materials with low-gravity and high intensity receive publicity (see, Patent document 1).
Due to cellulose nano-fibrous itself because comprising great amount of hydroxy group and hydrophily is high, they generally pass through The string comprising cellulose is made to carry out mechanical treatment acquisition at aqueous medium.But, due in water Solve fine to the cellulose nano-fibrous highly-hydrophilic obtained after nanometer level and by cellulose Nanowire Dimension forms network, so the viscosity of gained slurry and water-retaining property become high.Accordingly, there exist when by mistake Filter etc. makes cellulose nano-fibrous aqueous dispersions needs the drainage time extremely grown problem when being dehydrated.
Even if it addition, the consuming time obtained by drainage cellulose nano-fibrous after, if gained fiber Element nanofiber is finally dried, and makes them finally assemble due to the hydrogen bond between nanofiber, thus draws Act the problem being difficult to redisperse equably, although having relatively excellent dispersiveness in water.Therefore, very To being more difficult in high hydrophobicity resin the Composite that formation high-hydrophilic is cellulose nano-fibrous.Example As, although known before the drying by solvent displacement etc. by making sheet-like fiber element nanofiber take off Water, impregnated in subsequently in resin and makes cellulose nano-fibrous and resin compounded method (see, specially Profit document 2), but in the method, due to that of sheet form of being confined to cellulose nano-fibrous in resin A bit, accordingly, it is difficult to be uniformly dispersed nanofiber in resin.
[prior art literature]
[patent document]
[patent document 1] Japanese Unexamined Patent Application, JP 2005-42283 publication
[patent document 2] Japanese Unexamined Patent Application, JP 2006-241450 publication
[patent document 3] Japanese Unexamined Patent Application, JP 2010-168336 publication
Summary of the invention
The problem that invention is to be solved
It is an object of the invention to provide the modified fibre that drainage time is short when recycled fiber element nanofiber Element nanofiber, and there is high intensity and can make cellulose nano-fibrous dispersed after it reclaims The resin combination comprising modified cellulose nanofiber in resin.
For solving the scheme of problem
The inventors found that foregoing problems can be by with in anionic property additive and cationic Cellulose nano-fibrous solve.As the result of this neutralization, find when from aqueous medium recycled fiber element Drainage time during nanofiber shortens, and gained is cellulose nano-fibrous is homogeneously dispersed in moulding resin In, and the intensity of gained resin further enhances.
That is, the present invention relates to by with cellulose nano-fibrous with cationic in anionic property additive Cation group and the modified cellulose nanofiber that obtains.
Moreover, it relates to comprise the aforementioned modified cellulose nano-fibrous and resin combination of moulding resin Thing, and relate to the formed body obtained by being molded by resin combination.
Additionally, the present invention relates to the production method of modified cellulose nanofiber, it includes using anionic property Additive neutralizes the cation group that cationic is cellulose nano-fibrous.
The effect of invention
According to the present invention, the drainage time during can obtaining recycled fiber element nanofiber is greatly shortened and can The modified cellulose nanofiber that is readily dispersed in moulding resin, dispersed modified cellulose is had to receive The molding resin composition of rice fiber and the formed body of described composition.
Detailed description of the invention
Detailed description for carrying out the solution of the present invention presented below.
[cellulose nano-fibrous]
The cellulose nano-fibrous nanofiber being to derive from natural material of exploitation recently, and as having The resin composite of low-gravity and high intensity.In cellulose nano-fibrous production, typically via By means of with conche, high-pressure homogenizer, medium stirring mill machine, stone mortar, grinder or twin-screw extrusion Machines etc. grind and/or tap and make the material solution comprising cellulose fibre fibre or miniaturization receive to produce cellulose Rice fiber.The cellulose nano-fibrous known method such as Japanese Unexamined Patent Application that it be also possible to use is special The method described in 2005-42283 publication of opening produces.It is also possible to use it addition, cellulose nano-fibrous Microorganism (such as Acetobacter) produces.It addition, be used as the product being obtained commercially.Although comprising The source of the material of cellulose fibre is known includes plant (such as timber, bamboo, hemp, jute, South Africa Gombo hemp, crops rubbish, cloth, paper pulp, regenerated paper pulp or waste paper), animal (such as ascidian (squirt)), Algae, microorganism and microbial product, these sources any can be used in the present invention.Additionally, it is possible to make With cellulose (microfibrillated cellulose) the such as Sai Lisi of the micro-fibrillation being obtained commercially (Celish, Daicel Chemical Industries Ltd.).
The preferred origin of material comprising cellulose fibre comes from the cellulose fibre composition of plant or microorganism, And more preferably origin comes from the cellulose fibre composition of plant, its example being obtained commercially is KC Flock(NIPPON PAPER Chemicals Co.,Ltd.)。
It addition, cellulose nano-fibrous available bases solution (such as alkali metal hydroxide aqueous solution or ammoniacal liquor) Process.Obtain it addition, cellulose nano-fibrous also by following: the material comprising cellulose fibre First the shape that effective alkalis such as using conche, ball mill or shredding machine the most as required processes is being become With alkaline solution treatment after shape, then use the known solution used in cellulose nano-fibrous production fine or micro- Refinement technology (its representative instance includes using high-pressure homogenizer, medium stirring mill, stone mortar or grinder) grinds The product that mill and/or percussion process.
The cellulose nano-fibrous preferred 4nm to 800nm of diameter mean value, more preferably 4nm to 400nm, And even more preferably 4nm to 100nm.Although cellulose nano-fibrous have relative to fibre diameter the longest Fibre length and be difficult to measure its fibre length, but its mean value is preferably 5 times of fibre diameter Above, more preferably more than 10 times of fibre diameter, and more than 20 times of even more preferably fibre diameter. If having fibre length it addition, describe, then its preferred mean value is 50nm to 200 μm, and more preferably 100nm to 50 μm.
[cationic is cellulose nano-fibrous]
The cellulose nano-fibrous finger of cationic has been introduced into the cellulose nano-fibrous of cationic groups.Fine Dimension element is certainly as weak anionic, and cationic cellulose can obtain by processing with cationic agent ?.
Cationic groups refers to cation group and can become the group of cation group.Example includes season Ammonium salt, primary, secondary and tertiary amine, and hydrochloride and acetate.
Cationization can be carried out by known method.Cationic agent can be at the polysaccharide such as starch or cellulose Cationization in use any commonly employed cationic agent, condition is that cationic agent can cation Change this material, and the example of cationization method includes with glycidyltrialkylammonium ammonium halide or its halogen For alcohol, such as glycidyltrimetiiylammonium ammonium chloride (GTA) or 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride Process (seeing patent document 3).
Cationic cellulose nanofiber can be by receiving that the fiber of the fine cationization of solution usually obtains Rice fiber, and can after solving during fibre or solving fibre nanofiber described in cationization.
[cation ionization degree (cellulose degree of exchange)]
Cellulose cation ionization degree can be by measuring by the cationic groups of per unit cellulose glucose The degree of exchange that number represents is evaluated.Such as, when using glycidyltrimetiiylammonium ammonium chloride (GTA) conduct During cationic agent, cation ionization degree (cellulose degree of exchange) can be by measuring sample by means of chemiluminescence Nitrogen content uses following equalities to calculate.
Cation ionization degree=(162 × N)/(1400-151.6 × N)
N: nitrogen content (%)
In the cationic cellulose nanofiber of the present invention, although cation ionization degree is arbitrarily set, as long as its In the range of the effect not damaging the present invention, but preferably in the range of 0.01 to 0.5.
[the anionic degree of anionic property additive]
Anionic property additive in the present invention refers to have the anionic property that can neutralize cationic groups Group also preferably has the anionic property additive of more than 20mgKOH/g anionic degree.Owing to being used in this In the range of invention preferably, display can neutralize the anionic property interpolation of the anionic degree of cationic groups Agent processes the cationic groups that cationic is cellulose nano-fibrous, cationic cellulose Nanowire Dimension is assembled so that drainage, is thus preferred.Further, since come with this anionic property additive Modified cation is cellulose nano-fibrous, and cellulose nano-fibrous hydrophobic deg increases, and owing to recognizing For contributing to being homogeneously dispersed in resin when after drainage by cellulose nano-fibrous being redispersed in resin In so this is preferred.
[measurement of anionic degree]
The anionic degree of anionic property additive can be measured by various methods such as such as colloid measurements. In the present invention, anionic degree uses the PCD-02 charged particle analysis manufactured by Spectris Co., Ltd. Instrument measures.The explanation of measuring method presented below.
With ion exchange water dilution anionic property additive to after 0.02 weight %, take the moon of 10cc dilution from Sub-property additive is in the pond of PCD-02 analyzer.It follows that regulate to pH10 with ammonia spirit, The aqueous solution using 1/1000N poly-(diallyldimethylammonium chloride) (poly-DADMAC) carrys out titrated dilution Anionic property additive until streaming potential reaches zero.Anionic degree (the acid of anionic property additive Value) use equation as follows to be calculated by the titer of 1/1000mol/L poly-DADMAC solution.
The titer of anionic degree (mgKOH/g)=1/1000mol/L poly-DADMAC aqueous solution (ml)/2×56
[hydrophobic deg of anionic property additive]
In the anionic property additive of the present invention, preferably by having dredging in addition to anionic property group Drainage rate is improved at aqueous position.It addition, when will wherein use in anionic property additive and cationic When cellulose nano-fibrous modified cellulose nanofiber is redispersed in resin, owing to being typically considered that Contribute to being dispersed in the resin with hydrophobic deg higher than cellulose, it is advantageous to pass through anion Property additive shows a certain degree of hydrophobic deg.The hydrophobic deg of anionic property additive can be by HLB value table Show, and HLB value is preferably 1 to 15, and more preferably 1 to 10.
[calculating of hydrophobic deg]
In the present invention, the hydrophobic deg (HLB value) of anionic property additive can use Griffin (Griffin) method to use Following equalities calculates.
Hydrophobic deg (HLB value)=20 × (weight % of hydrophilic radical)
The hydrophilic radical of the present invention refers to polyoxyethylene chain, polyalcohol, acrylamide unit, maleic acid/richness horse Acid (salt) unit, (methyl) acrylic acid (salt) unit, itaconic acid (salt) unit, vinyl sulfonic acid (salt) unit, Vinyl phosphonate (salt) unit and (methyl) allyl sulphonic acid (salt) unit.
[kind of anionic property additive]
In the present invention, the instantiation of anionic property additive includes anionic property styrene resin, anion Property (methyl) acrylic resin, anionic property vistanex, anionic property polyester resin, rosin class With alkenyl succinate acids.These anionic property additives can be used alone or it multiple can use simultaneously.
Aforementioned anionic styrene resin is to have anionic property group and the water solubility of styrene main chain Or water-dispersed resin, the example includes styrene and the copolymer of anionic property unsaturated monomer.Cloudy from The partly or entirely available alkali metal such as potassium or sodium of sub-property group, alkaline-earth metal or ammonia, methylamine, ethamine, The amines such as dimethylamine, diethylamine, trimethylamine or triethylamine neutralize.Herein, cinnamic example Including styrene, AMS, the substituted AMS of alkyl, vinyltoluene and diethyl Alkenyl benzene.It addition, the example of anionic monomers include unsaturated monocarboxylic acid, unsaturated dicarboxylic, Unsaturated sulfonic acid and the copolymer of unsaturated phosphonic acids.Herein, the example of unsaturated monocarboxylic acid includes propylene Acid, methacrylic acid and crotonic acid, the example of unsaturated dicarboxylic includes maleic acid, maleic anhydride, richness Horse acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride, the example of unsaturated sulfonic acid includes ethene Base sulfonic acid, styrene sulfonic acid, (methyl) allyl sulphonic acid and 2-acrylamido-2-methyl propane sulfonic acid, Vinyl phosphonate and α-phenyl vinyl phosphonic acids is included with the example of unsaturated phosphonic acids.It addition, except aforementioned Component outside monomer also is used as the anionic property styrene resin of the present invention as required.
Aforementioned anionic (methyl) acrylic resin is for having anionic property group and (methyl) acrylic acid The water solubility of class main chain or water-dispersed resin, the example includes alkyl (methyl) acrylate and anion The copolymer of property unsaturated monomer.The all or part of available alkali metal such as potassium or sodium of anionic property group, The amines such as alkaline-earth metal or ammonia, methylamine, ethamine, dimethylamine, diethylamine, trimethylamine or triethylamine Neutralize.Herein, the example of alkyl (methyl) acrylate includes methyl (methyl) acrylate, ethyl (first Base) acrylate, normal-butyl (methyl) acrylate, isobutyl group (methyl) acrylate, the tert-butyl group (methyl) Acrylate, 2-ethylhexyl (methyl) acrylate, stearoyl (methyl) acrylate and cycloalkyl (first Base) acrylate.It addition, the example of anionic monomers includes unsaturated monocarboxylic acid, unsaturation two Carboxylic acid, unsaturated sulfonic acid and the copolymer of unsaturated phosphonic acids.Herein, the example bag of unsaturated monocarboxylic acid Including acrylic acid, methacrylic acid and crotonic acid, the example of unsaturated dicarboxylic includes maleic acid, maleic acid Acid anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid and citraconic anhydride, the example bag of unsaturated sulfonic acid Include vinyl sulfonic acid, styrene sulfonic acid, (methyl) allyl sulphonic acid and 2-acrylamido-2-methylpropane Sulfonic acid, and the example of unsaturated phosphonic acids includes vinyl phosphonate and α-phenyl vinyl phosphonic acids.It addition, remove Component outside aforementioned monomer also is used as anionic property (methyl) acrylic compounds of the present invention as required Resin.
The example of aforementioned anionic vistanex includes having anionic property group and alkene main chain Water-soluble or water-dispersed resin, the example includes by adding alkali compounds to by with unsaturation carboxylic Improved polyalkene that acrylic modified polyolefin obtains and be dissolved in the water or be dispersed in water those, and logical Cross and add alkali compounds to the modified polyolefin by making olefines and unsaturated carboxylic acid class copolymerization obtain Hydrocarbon and be dissolved in the water or be dispersed in water those.
It addition, when with unsaturated carboxylic acid class improved polyalkene or when combined polymerization olefines and unsaturated carboxylic acid Also dependent on needing to use the unsaturated monomer copolymerizable with unsaturated carboxylic acid class during class.Additionally, can mix Close different types of aforementioned polyolefins.
Herein, polyolefinic example includes the copolymer comprising at least alpha-olefin of ethene and propylene, and α- The example of alkene includes ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1- Nonene (1-nonene), 1-decene, 1-dodecylene (1-dodecene), 1-12 carbon decene (1-dodecadecene) and 4-methyl-1-pentene.The example of copolymer includes random copolymer, block copolymerization Thing, graft copolymer and mixture thereof.
The example of unsaturated carboxylic acid class includes unsaturated carboxylic acid, its derivative and unsaturated carboxylic acid anhydrides, and excellent Example is selected to include selecting the most unsaturated monoacid such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid； Unsaturated dibasic acid such as fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid And citraconic anhydride；Unsaturated dicarboxylic acid anhydride, the half ester of unsaturated dibasic acid, half acyl of unsaturated dibasic acid Amine；Unsaturated ternary acid such as aconitic acid, 3-butene-1,2,3-tricarboxylic acids and 4-amylene-1,2,4-tricarboxylic acids, Unsaturated tricarboxylic anhydride, the monoesters of unsaturated ternary acid and diester, the monoamides and two of unsaturated ternary acid Acid amides；Unsaturated tetra-atomic acid such as 1-amylene-1,1,4,4-tetrabasic carboxylic acid, 4-amylene-1,2,3,4-tetrabasic carboxylic acid and 3- Hexene-1,1,6,6-tetrabasic carboxylic acid；Unsaturated quaternary acid anhydrides, the unsaturated monoesters of tetra-atomic acid, diester and three esters, And at least one or two change of the group of the unsaturation monoamides of tetra-atomic acid, diamides and triamide composition Compound.
The example of copolymerizable unsaturated monomer includes (methyl) alkyl-acrylates such as acrylic acid first Ester, methyl methacrylate, ethyl acrylate, EMA, n-propyl, methyl N-propyl, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methyl-prop Olefin(e) acid N-butyl, isobutyl acrylate, Isobutyl methacrylate, acrylic acid 2-butyl ester, metering system Acid 2-butyl ester, tert-butyl acrylate, Tert-butyl Methacrylate, cyclohexyl acrylate, methacrylic acid Cyclohexyl, 2-EHA, 2-Ethylhexyl Methacrylate, n-octyl, methyl N-octyl, acrylic acid n-dodecane ester, methacrylic acid n-dodecane ester, acrylic acid positive 18 Alkyl ester and methacrylic acid n-octadecane ester；Styrene monomer such as styrene, AMS and Divinylbenzene, alkadiene class such as butadiene and isoprene；Diisobutylene；Vinyl esters such as second Vinyl acetate and propionate；With ethene ethers such as isobutylvinyl ether, dodecyl vinyl ether, Cyclohexyl vinyl ether, diglycol monotertiary vinethene and 4-hydroxyl butyl vinyl ether.It addition, other example includes (first Base) acrylic acid amides such as (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) acrylamide, N-alkyl (methyl) acrylamide and N, N-dialkyl group (methyl) acrylamide；(methyl) hydroxyalkyl acrylate example Such as (methyl) hydroxy-ethyl acrylate and (methyl) hydroxypropyl acrylate；(methyl) acrylic acid derivative is such as (methyl) alkyl acrylate epoxide alkyl ester, PAG (methyl) acrylate and PAG (first Base) acrylate alkyl ether.These ethylenically unsaturated compounds can be used alone or use two be can be combined Plant above type.
The example of alkali compounds includes alkali metal such as NaOH or potassium hydroxide；Alkaline-earth metal is such as Calcium hydroxide；With ammonium, methylamine, ethamine, propylamine, butylamine, hexylamine, octylame, monoethanolamine, isopropylamine, Propanolamine, 2-methyl-2-amino propyl alcohol, diethanol amine, N, N-dimethylethanolamine, N-methyl diethanol The amines such as amine, dimethylamine, triethylamine, morpholine, N-methylmorpholine and N-ethylmorpholine, and can use Its one or more types.
Aforementioned anionic polyester resin is to have anionic property group and the water solubility of polyester backbone or water Dispersion resin class, and the example includes by making as lactone compound anti-to hydroxycarboxylic acid addition Answer the terminal carboxylic of the polyester (or by the polyester making carboxyl acid component and alkoxide component reaction obtain) that product obtains All or part of, with the such as alkali metal such as potassium or sodium, alkaline-earth metal or such as ammonia, methylamine, ethamine, Dimethylamine, diethylamine, trimethylamine or triethylamine neutralize and give the resin of water solubility or water dispersible.
The hydroxyl of the aforementioned polyester obtained to the product of hydroxycarboxylic acid addition as lactone compound Carboxylic acids has hydroxyl and a carboxyl, and the example include glycolic, lactic acid, glyceric acid, hydroxybutyric acid, Malic acid, tartaric acid, citric acid, castor oil acid and hydroxy stearic acid.It addition, the reality of lactone compound Example include 4-methylcaprolactone, 2-methylcaprolactone, 6-caprolactone, δ-valerolactone, Beta-methyl-δ-valerolactone, Beta-propiolactone and gamma-butyrolacton.
Carboxyl acid component by making the polyester of aforementioned carboxylic acid's component and alkoxide component reaction acquisition is mainly made Known polyester raw material by the carboxylic acid form with more than divalent.The example of dibasic carboxylic acid includes aromatics dicarboxyl Acid such as terephthalic acids, isophthalic acid and adjacent phthalandione；Its acid anhydrides or its lower alkyl esters；Such as maleic acid, α, β-unsaturated dicarboxylic or its acid anhydrides such as fumaric acid, itaconic acid, mesaconic acid and citraconic acid；Such as the third two Aliphatic dicarboxylic acid or its acid anhydrides such as acid, butanedioic acid, glutaric acid, adipic acid, decanedioic acid or azelaic acid；With With the substituted butanedioic acid of the alkyl or alkenyl with 6 to 18 carbon atoms or its acid anhydrides.It addition, have trivalent The example of above carboxylic acid includes trimellitic acid, pyromellitic acid, tricarballylic acid and acid anhydrides thereof.
It addition, the purpose of the molecular weight or softening point in order to regulate resin as required can use unit price carboxylic Acid.The example of monovalent carboxylic includes the natural resin acid such as rosin class the most described or its modified shape Formula；The mono carboxylic acid of aliphatic series such as such as octanoic acid, capric acid, lauric acid/dodecanoic acid, myristic acid, palmitic acid or stearic acid； The such as one dollar aromatic carboxylic acid such as benzoic acid or naphthoic acid and derivative thereof.
It addition, for the alkoxide component mentioned by the polyester making carboxyl acid component and alkoxide component reaction obtain, main Use with the known polyester raw material with the alcohol form with more than divalent of the same way of carboxyl acid component. The example of dihydroxylic alcohols include such as ethylene glycol, 1,2-propane diols, 1,3-propane diols, 1,4-butanediol, new penta Glycol, 3-methyl isophthalic acid, 5-pentanediol, 1,6-HD, 1,8-ethohexadiol, diethylene glycol (DEG), triethylene glycol or hexamethylene Aliphatic or the alicyclic glycols such as alkane dimethanol；Such as polyoxypropylene (2.2)-2,2-is double (4-hydroxyphenyl) Double (4-hydroxyphenyl) propane of propane, polyoxypropylene (3.3)-2,2-, polyoxypropylene (2.0)-2,2-are double (4-hydroxyphenyl) Double (4-hydroxyphenyl) propane of propane, polyoxypropylene (2.0)-polyoxyethylene (2.0)-2,2-and polyoxypropylene (6) 2,2- The alkylene oxide adduct of the bisphenol-As such as double (4-hydroxyphenyl) propane.It addition, there is the alkoxide component of more than trivalent Example includes that trimethylolethane, trimethylolpropane, glycerine, 1,2,3,6-hexane tetrol, 1,4-are dehydrated Sorbierite, pentaerythrite, dipentaerythritol, tripentaerythritol, 1,2,4-butantriol, 1,2,5-penta triol, 2-methylpropane triol, 2-methyl isophthalic acid, 2,4-butantriol and 1,3,5-trihydroxytoluene.The most also can make Use hydroxycarboxylic acid.Instantiation includes P-hydroxybenzoic acid, citric acid and gallic acid.
Aforementioned rosin class is the such as raw pine lipid such as gum rosin, wood turpentine or tall oil rosin, or logical Cross and neutralize anionic property group with alkali metal or amines etc. and become the logical of water-soluble or water dispersible Cross and make feed purification, hydrogenation, be not homogenized or be polymerized various types of modified rosin classes of acquisition.Modified pine The example of lipid includes the camphine by obtaining by means of refined material rosin classes such as distillations, by making Hydrogenated rosins that the hydrogenation of raw pine lipid obtains, by making what raw pine lipid was not homogenized acquisition not to be homogenized pine Fat, by the polymerization rosin making raw pine lipid aggregate obtain, by by maleic acid, maleic anhydride, richness The unsaturated acids that the unsaturated acids modified feedstock rosin classes such as horse acid and (methyl) acrylic acid or modified rosin obtain Modified rosin (strengthening rosin), by phenols being added to the pinoresinol that raw material rosin or modified rosin obtain Class, by the methylolation product of phenols is added to rosin that raw pine lipid or modified rosin obtain with And by making raw material rosin and alcohol react the rosin esters of acquisition.In these, preferably by with amines Or the water-soluble rosin metal obtained with raw material rosin or modified rosin class in the such as alkali metal such as potassium or sodium Salt.
Foregoing alkenyl succinic acids be by with alkali metal or such as ammonia, methylamine, ethamine, dimethylamine, two In the amines such as ethamine, trimethylamine or triethylamine and all or part of carboxyl of alkenyl succinic acid and give Those of water-soluble or water dispersible, or by with in alkali metal or amines and anionic property group and Give half ester or half acyl of the alkenylsuccinic derivatives such as alkenyl succinic acid of water solubility or water dispersible Amine.The example of foregoing alkenyl butanedioic acid includes hexenyl succinic acid, ocentyl succinic, laurylene base amber Amber acid, hexadecylene base butanedioic acid and octadecenyl succinic acid.
[with the neutralization of anionic property additive]
Method for neutralizing cationic cellulose nano-fibrous with anionic property additive is included in Anionic property additive is added cellulose nano-fibrous to cationic while being scattered in aqueous medium. By by means of the anionic property additive using stirring vane etc. to carry out uniform mixed anion additive And neutralize all or part of of the cellulose nano-fibrous cationic groups of cationic, thus obtain The modified cellulose nanofiber assembled in water.When the cationic base that cationic is cellulose nano-fibrous When the anionic property group of group's anionic property additive neutralizes, only a part cationic base can be neutralized Group maybe can neutralize whole cationic groups.Neutralize cationic cellulose nano-fibrous whole positive from In the case of sub-property group, the interpolation number of the anionic property group of anionic property additive can be more than cation The number of the cationic groups that property is cellulose nano-fibrous.
[the cellulose nano-fibrous ratio with anionic property additive of cationic]
In the present invention, although for the compounding that anionic property additive and cationic are cellulose nano-fibrous Ratio is not particularly limited, as long as it is allowing to obtain in the range of the effect of the present invention, and anionic property The incorporation of additive is preferably 1 weight portion to 200 weight portions more preferably 5 weight portions to 100 weight portions, Cellulose nano-fibrous based on 100 weight portion cationic.
[modified cellulose nanofiber]
Modified cellulose nanofiber in the present invention can by with the moon of aforementioned anionic additive from Cationic groups cellulose nano-fibrous with aforesaid cations in sub-property group obtains.Due to sun The cationic groups of ionic cellulose element nanofiber and the anionic property group of anionic property additive Become electroneutral in an aqueous medium, so cationic is cellulose nano-fibrous and anionic property additive Form complex, and this becomes modified cellulose nanofiber.
The cellulose nano-fibrous neutralization by anionic property additive of cationic can add by measuring Add ζ (zeta) current potential of the cellulose nano-fibrous aqueous medium of cationic before and after anionic property additive to come Confirm.Such as to, anionic property additive is added the cellulose nano-fibrous aqueous medium of cationic, And remove remaining anionic property additive by suction filtration.Then neutralizing can be by measuring by making The change of the zeta potential obtaining the dispersion liquid that modified cellulose nanofiber is redispersed in water obtaining confirms.
It addition, modified cellulose nanofiber is next really also by the anionic property additive of detection Composite Recognize.
Such as, after processing modified cellulose nanofiber with watery hydrochloric acid, Solvent Extract methods acid treatment is used Modified cellulose nanofiber, and its concentrate can carry out various types of analysis (such as, FT-IR or Utilize the ionic survey being used for measuring the charged particle analyzer of the anionic degree of anionic property additive Amount) to confirm that modified cellulose nanofiber comprises anionic property additive.
It addition, the existence in the existence of cellulose and nitrogen source can be by the residue after analysis Solvent Extract methods (by FT-IR or elementary analysis etc.) confirm, result thus allows to confirm depositing of cationic cellulose ?.
[recovery of modified cellulose nanofiber]
For reclaiming by with in anionic property additive and cationic cellulose nano-fibrous acquisition The separable solid existed in an aqueous medium of the method for modified cellulose nanofiber, and example bag Include filtration, press filtration and centrifugation.
[incorporating modified cellulose nano-fibrous in resin]
The modified cellulose nanofiber reclaimed from aqueous medium by drainage is preferably incorporated into shaping In resin.The example of moulding resin includes thermosetting resin and thermoplastic resin.
[thermosetting resin]
Thermosetting resin is gone up substantially and does not limit, and known thermosetting resin can be used.
The example of spendable thermosetting resin include phenolic resin, urea resin, melmac, Unsaturated polyester resin, epoxy resin, dially phthalate resin, polyurethane resin, silicon resin and poly- Imide resin.Can be used alone a kind of resin or the combined resin using more than two types.Preferably Phenolic resin, epoxy resin and unsaturated polyester resin.
[thermoplastic resin]
Thermoplastic resin is gone up substantially and does not limit, and known thermoplastic resin can be used.Example Thermoplastic resin including the such as vistanex such as polyethylene and polypropylene form；The most poly-terephthaldehyde The acid polyester resin such as second diester and polybutylene terephthalate；Such as polymethyl methacrylate and poly-first The acrylic resins such as base ethyl acrylate；Such as polystyrene, acrylonitrile-butadiene-styrene resin, Acrylonitrile-acryl rubber-styrene resin, acrylonitrile-vinyl rubber-styrene resin, (methyl) The styrene resin lipids such as Acrylate-styrene bipolymer resin and s-B-S resin；Such as from The polyamides such as copolymer resin, polyacrylonitrile and nylon；Ethylene vinyl acetate resin, ethylene-propylene Acid resin, ethylene-ethylacrylate resin, ethylene-vinyl alcohol resin；Such as polyvinyl chloride and poly-inclined two The chlorinated resins such as vinyl chloride, the such as fluororesin such as polyvinyl fluoride and polyvinylidene fluoride；Such as Merlon The thermoplastic resins such as resin, modified poly (phenylene ether) resin, methylpentene resin and celluosic resin； Such as olefin-based elastomer, chlorinated ethylene based elastomers, styrene series elastomer, polyurethane series elasticity More than the thermoplastic elastomer (TPE)s, and its two types such as body, polyester-based elastomer or polyamide-based elastomer Mixture.
[modified cellulose nanofiber mixes moulding resin]
For being not particularly limited for incorporating modified cellulose nano-fibrous method in moulding resin, Although moulding resin can be impregnated with sheet material or the aggregation of modified cellulose nanofiber, can by shaping tree Fat adds modified cellulose nanofiber dispersion liquid in an aqueous medium to and filters subsequently and be dried, can be by The wet cake of modified cellulose nanofiber is incorporated in moulding resin and is subsequently dried, maybe can be by dry modified fine Dimension element nanofiber adds moulding resin to and mixes subsequently, but if uses and wherein added by moulding resin To the modified cellulose nanofiber drainage subsequently being scattered in aqueous medium and be dried method, then due to Mixing with resin and drainage and drying steps can be carried out continuously, so modified cellulose nanofiber can It is scattered in moulding resin and does not use the such as hydrophilic solvent such as alcohol or ether or such as hexane or acetic acid alkyl The organic solvent of the form of the hydrophobic solvents such as ester, its result, it is no longer necessary to the steps such as such as solvent displacement, And technique becomes extremely simple, thus makes it particularly preferred.
Modified cellulose nanofiber is preferably mixing with moulding resin to help mixing therein while In the dispersion in moulding resin of the modified cellulose nanofiber, and by modified cellulose nanofiber It is scattered in the case of thermoplastic resin, is preferably used, such as double screw extruder, internal mixer (internal mixer) or blender (blender).
[resin combination]
Resin combination in the present invention comprises by with anionic property additive treating cationic fiber The modified cellulose nanofiber that element nanofiber obtains, and moulding resin.When moulding resin is 100 weights When measuring the amount of part, modified cellulose nanofiber content in resin combination is preferably 0.5 weight portion extremely 90 weight portions, more preferably 5 weight portions are to 50 weight portions, and even more preferably 5 weight portions are to 30 weight portions. If cellulose nano-fibrous content is below 0.5 weight portion, then tend to becoming to be difficult to show that cellulose is received The strengthening effect of rice fiber.Although the resin combination of the present invention can be directly used for composition or solidification is produced Thing, but it also can be by coming as masterbatch with other resins dilute.
[additive of resin combination]
Resin combination in the present invention also can comprise various types of additive, only its they do not damaging Add in the range of the effect of the present invention.The example of the additive that can mix includes that organic or inorganic is filled out Material, pigment, thickener, viscosity reducers, plasticizer, fast light additive (such as ultra-violet absorber Or stabilizer), antioxidant, ozonisation preventing agent, activator, antistatic additive, lubricant, antifriction Liniment, surface conditioner (such as levelling agent, defoamer and anticaking agent), mould inhibitor (anti-mold agent), Antiseptic, dispersant, fire retardant, vulcanization accelerator and vulcanization accelerator additive.Can be used alone, these add Add a type of agent or use two types more than be can be combined.
[production of formed body]
The resin combination of the present invention is generally used for the method for molding resin composition, example known to can using Such as compression forming, injection moulding, extrusion molding or foaming.As desired by suitably regulating resin Condition of molding adapts to condition of molding.
[purposes of formed body]
Owing to it is lightweight and intensity is high, the resin-formed body comprising modified cellulose nanofiber of gained Can be used for, wherein use the formed body of the string (cellulose nano-fibrous) of conventional micro-fibrillation With the field of the resin-formed body of the string comprising micro-fibrillation, and need more high mechanical properties The field of (the most curved by intensity).Such as, the formed body comprising modified cellulose nanofiber of gained can It is efficiently used for the internals of conveying arrangement, the external members such as such as automobile, train, boats and ships or aircraft And structural elements, the such as housing of electric product such as PC, TV or phone, structural material and interior Parts, construction material, stationery material, the housing of the office device such as such as OA device, sports and amusement Articles for use and structural material.
[embodiment]
The explanation of the present invention is given below by embodiment.Unless additionally specifically indicated that, otherwise term " part " and " % " is based on weight.
[anionic property additive]
Anionic property additive for the present invention is shown in table 1 below.
[table 1]
A-1:SEIKO PMC CORP., the polyolefin emulsion " VE-1217 " that acid is modified
The neutralization aqueous solution (Mw:8,500) of A-2: styrene-maleic anhydride copolymer
The neutralization aqueous solution (Mw:40,000) of A-3: Styrene-acrylic copolymer
A-4:SEIKO PMC CORP., the polyolefin emulsion " ZE-1478 " that acid is modified
A-5: butyl methacrylate copolymer (Mw:10,000)
A-6:SEIKO PMC CORP., the strengthening rosin of neutralization, " FR-1900 "
A-7: the anionic property polyester resin described in following synthesis example 1
A-8: the alkenyl succinate acids described in following synthesis example 2
A-9:SEIKO PMC CORP., anionic property polyacrylamide resin, " DA4160 "
[calculating of anionic degree]
Use the PCD-02 charged particle analysis-e/or determining anionic manufactured by Spectris Co., Ltd. Degree.The explanation of measuring method is given below.
With after ion exchange water dilution anionic property additive to 0.02 weight %, take its 10cc equal sample Product are in the pond of PCD-02.With after ammonia spirit regulation to pH10, use poly-(two allyls of 1/1000N Base alkyl dimethyl ammonium chloride) (poly-DADMAC) aqueous solution titrated dilution anionic property additive until flowing Current potential reaches zero.The anionic degree (acid number) of anionic property additive is gathered by 1/1000mol/L The titer of the DADMAC aqueous solution uses equation shown below to calculate.
The titer of anionic degree (mgKOH/g)=1/1000mol/L poly-DADMAC solution (ml)/2×56
[calculating of hydrophobic deg]
In the present invention, the hydrophobic deg of anionic property additive uses Griffin method to utilize following equalities to count Calculate.
Hydrophobic deg (HLB value)=20 × (weight % of hydrophilic radical)
(hydrophilic radical of the present invention refers to polyoxyethylene chain, polyalcohol, acrylamide unit, maleic acid/fumaric acid (salt) Unit, (methyl) acrylic acid (salt) unit, itaconic acid (salt) unit, vinyl sulfonic acid (salt) unit, ethene Base phosphoric acid (salt) unit and (methyl) allyl sulphonic acid (salt) unit.)
(synthesis example 1)
The synthesis of anionic property polyester resin anionic property additive A-7
300.5g12-hydroxy stearic acid, 114.2g epsilon-caprolactams and 0.28g butyl titanate are put into outfit Have in the 500ml volume glass container of agitator, in heating while stirring in the presence of nitrogen stream subsequently Inclusion is to 160 DEG C.At a temperature of 160 DEG C, keep inclusion after 3 hours, cooling inclusion to 100 DEG C, with Rear taking-up inclusion is also cooled further to room temperature to obtain faint yellow solid resin.
98.4g aforesaid solid resin is put into equipped with in the 500ml volume glass container of agitator, subsequently Add 53.5g dimethylethanolamine further and heat inclusion extremely while stirring in the presence of nitrogen stream 70℃.Keep inclusion after 30 minutes at a temperature of 70 DEG C, add 355g ion exchange water and have to obtain The concentration of 20 weight % and the aqueous dispersions of the anionic property polyester resin of 230mPas viscosity.
(synthesis example 2)
The synthesis of alkenyl succinic acid anionoid additive A-8
106.4g dodecyl succinic anhydride and 43.4g phenmethylol are added to equipped with agitator 1000ml volume glass container adds the 0.36g concentrated sulfuric acid subsequently and heats inclusion extremely while stirring 70℃.The temperature keeping inclusion after 2.5 hours, adds 42g48 weight % potassium hydroxide water-soluble in 70 DEG C Liquid, 356g ion exchange water and 19.2g diethylene glycol dimethyl ether with obtain have 25 weight % concentration, The viscosity of 190mPas and the aqueous dispersions of the alkenyl succinate acids of pH10.
(producing example 1)
The production of cationic cellulose nano-fibrous 1
[preparation of cationic cellulose 1]
By 100g KC Flock W50GK (cellulose powder, NIPPON PAPER Chemicals Co., Ltd.) the comprise fibrous material of cellulose, 770g ion exchange water and the 3387g isopropanol of form is put into and is joined Have the inclusion being gently stirred for 5L volume glass container in the 5L volume glass container of agitator subsequently And add 38.9g sodium hydrate aqueous solution (concentration: 30 weight %) further to its inclusion.At 30 DEG C The inclusion after 30 minutes of stirring 5L volume glass container, temperature is risen to 75 DEG C with after will through 15 minutes The cationization of 250g glycidyltrimetiiylammonium ammonium chloride (GTA) aqueous solution (concentration: 80 weight %) form The inclusion to 5L volume glass container is added in agent.Add from GTA to cool down after starting 2 hours in the past and include Thing, neutralizes 5L volume glass flask by being added to 90.6g hydrochloric acid (concentration: 10 weight %) subsequently Inclusion.
After filtering neutralized inclusion, permeate is put in 5L volume glass container to remove remnants' Water soluble chemicals adds about 5000g ion exchange water the most further to 5L volume glass container, stirring The inclusion of 5L volume glass container repetition filter operation 3 times after agitation.455g is obtained from GTA The filtration residue (concentration: 21.4 weight %) of the slurry form of the cationic cellulose 1 of cationization.
[solution of cationized cellulose 1 is fine]
7700g ion exchange water is added to 300g and is adjusted to the gained cation chemical fibre of 20 weight % concentration With the preparation gross weight aqueous suspension as 8000g, (cationic cellulose 1 slurry has the slurry of dimension element 1 The concentration of 0.75 weight %).Gained slurry is under the following conditions by ball mill (model: ECM-Pilot, Willie Et Bakkofen Corp.) carry out machinery solution fibre, to obtain the slurry of cationic cellulose nano-fibrous 1 (concentration: 0.75 weight %).The cation ionization degree measured under conditions of shown below is 0.05.
<solution fibrid>
Pearl kind: zircon pearl (diameter: 0.5mm)
Vessel volume: 1.5 liters
Pearl loading: 2470g
Cellulose paste flow velocity: 2800g/min
Peripheral speed: 13m/s
Container cooling water temperature: 8 DEG C
The process time: 30 minutes
<measurement of cation ionization degree>
By using by MITSUBISHI CHEMICAL ANALYTECH Co., Ltd. manufacture The nitrogen content that the total blood urea/nitrogen analyzer of TN-110 is measured sample by chemiluminescence calculates cation according to following equalities Change degree (GTA adding rate).
Cation ionization degree=(162 × N)/(1400-151.6 × N)
N: nitrogen content (%)
[observation of cationized cellulose nanofiber]
Weigh up the slurry of about 10g gained cationized cellulose nanofiber 1 and by being added to The dilution of 100g ethanol is stirred 5 minutes with magnetic stirrer subsequently.The slurry of dilution is at 10000rpm and 5 DEG C Centrifugal (Himac CR22GII type, Hitachi Koki Co., Ltd.) 5 minutes, and remove supernatant by decantation Liquid.After repetition same operation twice, the interpolation tert-butyl alcohol is to residue ad pond om 50g, the most at room temperature Stirring, to obtain uniform sizing material, is then centrifuged.After repetition same operation twice, carry out with the tert-butyl alcohol The residue liquid nitrogen frozen of solvent displacement, and obtained by freeze-drying (VD-250F type, Taitec Corp.) Obtain the powder of cationic cellulose nano-fibrous 1.
Gained cationic is observed fine under using Field Emission Scanning Electron microscope in 30000 × multiplying power During the form of powder of dimension element nanofiber 1, it was observed that there is the cellulose nanometer of about 10nm fibre diameter Fiber.
(manufacturing example 2)
Untreated cellulose nano-fibrous production
[solution of untreated cellulose is fine]
7940g ion exchange water is added to 60g KC Flock W50GK (cellulose powder, NIPPON PAPER Chemicals Co., Ltd.) form the fibrous material comprising cellulose with preparation gross weight be The aqueous suspension (there is the cellulose paste of 0.75 weight % concentration) of 8000g.With produce described in example 1 Solve under conditions of the solution fibrid of cationic cellulose is identical fine gained cellulose paste to obtain at The cellulose nano-fibrous slurry (concentration: 0.75 weight %) of reason.
[cellulose nano-fibrous observation]
Weigh up the cellulose nano-fibrous slurry of about 10g gained and dilute by being added to 100g ethanol Stir 5 minutes with magnetic stirrer subsequently.The slurry of dilution is centrifugal (Himac at 10000rpm and 5 DEG C CR22GII type, Hitachi Koki Co., Ltd.) 5 minutes, and remove supernatant by decantation.Repeat phase After biconditional operation twice, the interpolation tert-butyl alcohol, to residue ad pond om 50g, is stirred at room temperature to obtain subsequently Uniform sizing material, is then centrifuged.After repetition same operation twice, carry out solvent displacement with the tert-butyl alcohol Residue liquid nitrogen frozen, and received by freeze-drying (VD-250F type, Taitec Corp.) acquisition cellulose Rice fiber dust.
Observe cellulose nano-fibrous under using Field Emission Scanning Electron microscope in 30000 × multiplying power During the form of powder, it was observed that there is the cellulose nano-fibrous of about 10nm fibre diameter.
(producing example 3)
The production of cationic cellulose nano-fibrous 2
[cellulose nano-fibrous cationization]
Untreated cellulose nano-fibrous slurry that 2000g is obtained by manner described above (concentration: 0.75 weight %) it is concentrated into 125g by filtration under diminished pressure, and put into the 1L volume glass appearance equipped with agitator Device adds 5.5g ion exchange water and 508g isopropanol subsequently, is gently stirred for, and adds further 5.84g sodium hydrate aqueous solution (concentration: 30 weight %).
After the inclusion 30 minutes of 30 DEG C of stirring 1L volume glass containers, be warming up to 75 DEG C further Add the cationic agent of the 37.5g GTA aqueous solution (concentration: 80 weight %) form.Mistake after adding GTA Cool down inclusion after going 2 hours, be then added to 13.9g hydrochloric acid (concentration: 10 weight %), to obtain sun Ionic cellulose element nanofiber 2.
Sun is reclaimed by the water slurry (7500rpm, 20 minutes) of centrifugal cationic cellulose nano-fibrous 2 Ionic cellulose element nanofiber 2, and 1000g ion exchange water is further added to gained sediment with Rear stirring.This operation is repeated twice and adjusts to the sediment being centrifuged rear gained by adding ion exchange water Joint concentration, thus obtain the slurry (concentration: 0.75 weight %) of cationic cellulose nano-fibrous 2.
(embodiment 1)
The production of modified cellulose nanofiber and drainage tests
By the moon of 37.5g anionic property additive A-1 (SEIKO PMC CORP., " VE-1217 ") form from The dilution (concentration: 1 weight %) of sub-property additive adds 50g to and produces the cationic fibre obtained in example 1 The slurry of dimension element nanofiber 1 is so that the amount of anionic property additive is relative to 100 weight portion cationic The solid composition of cellulose nano-fibrous form is 10 weight portions；Magnetic stirrer and stirring rod is used to stir subsequently Mix 10 minutes with the cluster (flock) forming modified cellulose nanofiber, this cluster is by with anionic property Agent neutralizes the cellulose nano-fibrous acquisition of cationic；It is derived from comprising modified cellulose and receives material fiber collection The slurry of group.The slurry that gained comprises modified cellulose nanofiber cluster uses Nutsche filter (mistake Filter diameter: 55mm), filter paper (No.2,55mm, Advantec Co., Ltd.), filter flask and aspirator (aspirator) (WJ-20, final vacuum: 23.3hPa (20 DEG C), Sibata Scientific Technology, Ltd.) carry out filtration under diminished pressure.Measure until filtrate time of no longer dripping during 30 seconds Amount, is used as the value of drainage time.Result is shown in Table 2.
(embodiment 2 to 38 and comparative example 1 to 3)
Operation same as in Example 1 is used to prepare modified cellulose Nanowire with the compounding ratio shown in table 2 Dimension, result is shown in Table 2.But, the drainage time feelings more than 3600 seconds during drainage time is measured Condition is evaluated as "×".
[table 2]
(embodiment 39)
Confirm to neutralize by measuring zeta potential
Based on cellulose nano-fibrous solid composition with 10 weight % by anionic property additive A-2 form Anionic property additive add to produce example 1 obtain the cellulose nano-fibrous slurry of cationic (concentration: 0.75 weight %), after using magnetic stirrer and stirring rod to stir at 25 DEG C 5 minutes, use SPZ06 ζ The zeta potential of gained modified cellulose nanofiber measured by potentiometric analyzer (Spectris Co., Ltd.).Measure Value is+18mV.With above-mentioned independently, when without in the case of anionic property additive measure time Zeta potential is+80mV.Confirm the measured value interpolation speed corresponding to anionic property additive A-2 of zeta potential Rate fluctuates to its minus side from+80V.
(embodiment 40)
FT-IR is used to be identified through the neutralization of anionic property additive
Based on cellulose nano-fibrous solid composition with 100 weight % by anionic property additive A-2 form Anionic property additive add 200g to and produce the cationic cellulose nano-fibrous 1 that example 1 obtains The dilution (concentration: 0.15 weight %) of slurry, uses magnetic stirrer and stirring rod to stir subsequently at 25 DEG C Mix 5 minutes to produce modified cellulose nanofiber.Use Buchner funnel (Advantec Toyo Kaisha, Ltd., use No.2 filter paper, filter paper diameter: 90mm) gained modified cellulose nanofiber is entered Row suction filtration.It follows that filter residue to be transferred to 500ml beaker, add subsequently aqueous hydrochloric acid solution (concentration: 1 weight %) ad pond om 300g, use magnetic stirrer and stirring rod stirring after, take 100g sample and with Above-mentioned identical mode is filtered by suction.
It addition, gained filter residue transfers to the 300mL volume glass container equipped with agitator, and adding After 100g toluene, heat at 90 DEG C and stir 2 hours and cool down, in the same way as described above It is filtered by suction.From the toluene of gained filtrate mutually distill toluene, and be dried under reduced pressure gained first After benzene extractives, use Spectrum One fourier transform infrared spectroscopy instrument (PerkinElmer Japan Co., Ltd.) carry out FT-IR measurement to deriving from the toluene extract that modified cellulose nanofiber is dried (cumulative frequency (integration cycle): 32).
Similarly, aqueous hydrochloric acid solution (concentration: 1 weight %) is added to anionic property additive A-2 dilute Release liquid (concentration: 3 weight %) until pH is reduced to 3.8 by 10, and use magnetic stirrer and stirring rod After stirring 5 minutes, it is dried under reduced pressure filter residue and is filtered by suction in the same manner as described above, with Rear use Spectrum One fourier transform infrared spectroscopy instrument (PerkinElmer Japan Co., Ltd.) is right The anionic property additive FT-IR being dried measures (cumulative frequency: 32).
When derive from modified cellulose nanofiber aforementioned toluene extract IR measurement result with cloudy from When the IR measurement result of sub-property additive compares, extract at the toluene deriving from modified cellulose nanofiber The IR figure of thing observes the peak being attributable to anionic property additive, thereby confirms that and added by anionic property Agent neutralizes modified cellulose nanofiber.
It addition, the filter residue obtained after the toluene at modified cellulose nanofiber extracts is equally by FT-IR During measurement, confirm the existence of cellulose.
(embodiment 41)
Comprise the production of the cellulose nano-fibrous resin combination of modification
With the solid composition cellulose nano-fibrous relative to 5 weight portion cationic be 5 weight portions cloudy from The ratio of the solid composition of sub-property additive adds the anionic property of 6000g anionic property additive A-1 form The dilution of additive (Gu composition: 1 weight %) produces, to 8000g, the modified cellulose Nanowire that example 1 obtains After the slurry (concentration: 0.75 weight %) of dimension 1, use Polytron homogenizer (model: PT3100, Kinematica AG) and Eurostar numeral agitator (IKA Werke GmbH Co.) combination stirring institute Obtaining mixture 10 minutes, to form the cluster of modified cellulose nanofiber, (it is by adding with anionic property Add agent and neutralize that cationic is cellulose nano-fibrous obtains)；It is derived from comprising modified cellulose nanometer The slurry of fiber.
By the moulding resin of 1200g polypropylene powder resin form (H-700, Prime Polymer Co., Ltd.) It is 100 weight portion moulding resins with the solid composition cellulose nano-fibrous relative to 5 weight portion cationic Ratio add the slurry comprising modified cellulose nanofiber cluster to, stirring 10 minutes the most further To obtain the slurry of the resin combination comprising modified cellulose nanofiber.
With Nutsche filter (filter diameter: 185mm) and filter flask, use aspirator (model: WJ-20, final vacuum: 23.3hPa (20 DEG C), Sibata Scientific Technology, Ltd.) make before State the slurry of the resin combination comprising modified cellulose nanofiber carry out filtration under diminished pressure (nylon cloth, 110 Sieve mesh) after, adding filter-press residues to water content is below 40 weight %, thus obtains and comprise modified cellulose nanometer The wet cake of the resin combination of fiber.
Compounding ratio shown below and evaluation of physical properties result are shown in table 3 and 4.
[being dried of the resin combination comprising modified cellulose nanofiber]
The wet cake of the aforementioned resin combination comprising modified cellulose nanofiber is put into twin-screw squeeze Go out machine (screw diameter: 15mm, Technovel Corp.), be dried process subsequently.Squeezed by twin-screw The drying condition going out machine use is as follows.
<drying condition>
Screw diameter: 15mm
Screw rod rotary speed: 200rpm
L/D:45
Discharge rate: 300 to 400g/hr (as solid composition)
Arrange temperature: C1 (100 DEG C), C2 (100 DEG C), C3 (100 DEG C), C4 (90 DEG C), C5 (90 DEG C), C6(90℃)
[modified cellulose nanofiber in moulding resin dispersed]
Comprise the resin combination double screw extruder being dried of modified cellulose nanofiber melted and Mixing and use granulator (model: VC, Nakatani Kikai Co., Ltd.) granulating (size: about 1.5mm × 1.5mm), thus obtain the particle that wherein disperse modified is cellulose nano-fibrous.Melted and mixed Refining condition is as follows.
<melted and compounding conditions>
Screw diameter: 15mm
Screw rod rotary speed: 200rpm
Discharge rate: about 1000g/hr
Design temperature: C1-C6 (200 DEG C), H/D (200 DEG C)
[scattered evaluation]
Weigh the cellulose nano-fibrous particle of about 0.5g wherein disperse modified and by stainless steel flat plate Between clamping and hot pressing (by melted (200 DEG C) → roll (pressure: 10kg/cm2, the retention time: 30 seconds) → Cooling (25 DEG C) composition) it is shaped to the membranaceous of thickness about 0.1mm, thus obtain wherein disperse modified cellulose The film of nanofiber.The presence or absence of cellulose nano-fibrous thick aggregation present in visualization gained film To evaluate the dispersiveness of modified cellulose nanofiber in moulding resin.When will wherein not observe in film When situation to aggregation is evaluated as "○" and the situation wherein observing aggregation is evaluated as "×"；? The film being wherein dispersed with modified cellulose nanofiber obtained in embodiment 41 is not observed thick poly- Collective, is evaluated as zero by this film.
[production of formed body]
Particle cellulose nano-fibrous for wherein disperse modified is put into injection (mo(u)lding) machine (Minimat 14/7B, Sumitomo Heavy Industries, Ltd.), and inject there is 3mm thickness, 12.5mm The plate type metal mould of width and 75mm length, thus obtain formed body test film (shaping temperature Degree: 180 DEG C to 185 DEG C, metal die temperature: 30 DEG C).
[bending strength and bending (measurement of (elastic) modulus]
Bending strength (MPa) and the bending (elastic) modulus (MPa) of afore-mentioned test sheet are tested at 10mm/min Use under speed and 50mm pivot distance Tensilon universal testing machine (Toyo Baldwin Co., Ltd., negative He Chi (load cell): 500kg) measure.
[measurement of Izod impact values]
Use scoring tool (notching tool) (model: A-3, V-type cutting sheet, Toyo Seiki Kogyo Co., Ltd.) indentation of the making 3.3mm degree of depth in afore-mentioned test sheet.Then izodtest is used The Izod impact values of the test film of indentation measured by machine (1J hammers into shape, Toyo Seiki Kogyo Co., Ltd.) (kJ/m2, 23 DEG C).
(embodiment 42 to 50 and comparative example 4 to 7)
In addition to becoming the ratio of the compounding shown in table 3 below, carry out the operation of embodiment 41 in an identical manner； Disperse with post-evaluation.Then the bending measuring the test film that dispersion is evaluated as those good embodiments is strong Degree, the modulus of elasticity in static bending and Izod impact values.Result is shown in table 3 and 4.
[table 3]
[table 4]
(producing example 4)
The production of cationic cellulose nano-fibrous 3
[preparation of cationized cellulose 2]
The fibre comprising cellulose by 800gLBKP (hardwood kraft pulp, concentration: 20 weight %) form Dimension material and 2175g isopropanol are put into equipped with in the 5L volume glass container of agitator, the most leniently The inclusion of stirring 5L volume glass container add further 58.4g sodium hydrate aqueous solution to it (dense Degree: 30 weight %).At 30 DEG C, the inclusion of stirring 5L volume glass container is after 30 minutes, is warming up to 75 DEG C, with after through 20 minutes add 1875g glycidyltrimetiiylammonium ammonium chloride (GTA) aqueous solution form The cationic agent of (concentration: 80 weight %) is to the inclusion of 5L volume glass container.Add from GTA and open Begin to cool down after 2 hours in the past inclusion, use hydrochloric acid (concentration: 10 weight %) to regulate 5L volume glass subsequently The inclusion of flask is to pH7.
After filtering neutralized inclusion with 200 sieve mesh filter cloths, permeate is put into 5L volume glass and holds To remove remaining water soluble chemicals in device, add about 4000g ion exchange water the most further to 5L Volume glass container, the inclusion of stirring 5L volume glass container repetition filter operation two after agitation Secondary.Interpolation 3000g isopropanol is to filter residue further, is subsequently agitated for the inclusion of 5L volume glass container also Filter after agitation.The full dose of aforementioned filter residue adds the 5L equipped with agitator together with 2175g propyl alcohol to Volume glass container, is gently stirred for the inclusion of 5L volume glass container subsequently and is added to 58.4g Sodium hydrate aqueous solution (concentration: 30 weight %).The inclusion of 5L volume glass container is stirred at 30 DEG C After 30 minutes, be warming up to 75 DEG C, with after through 20 minutes add 1875g glycidyltrimetiiylammonium ammonium chloride (GTA) cationic agent the including to 5L volume glass container of the aqueous solution (concentration: 80 weight %) form Thing.Add from GTA and cool down inclusion after starting 2 hours in the past, use hydrochloric acid (concentration: 10 weight subsequently %) inclusion of regulation 5L volume glass flask is to pH7.
After filtering neutralized inclusion with 200 sieve mesh filter cloths, permeate is put into 5L volume glass and holds To remove remaining water soluble chemicals in device, add about 4000g ion exchange water the most further to 5L Volume glass container, the inclusion of stirring 5L volume glass container repetition filter operation three after agitation Secondary.Then regulate concentration by interpolation ion exchange water to filter residue, thus it is fine to obtain 13kg cationic The slurry (concentration: 1.0 weight %) of dimension element 2.The degree of exchange of this cationic cellulose 2 is 0.15.
[solution of cationized cellulose 2 is fine]
3000g ion exchange water is added to 3000g and regulates the cationization fiber to 1.7 weight % concentration The slurry of element 2, is diluted to the concentration of 0.85 weight % subsequently.Under the following conditions with ball mill (model: ECM-Pilot, Willie et Bakkofen Corp.) gained slurry carried out machinery solve fibre, with obtain sun from The slurry (concentration: 0.85 weight %) of sub-property cellulose nano-fibrous 3.
<solution fibrid>
Pearl kind: zircon pearl (diameter: 0.5mm)
Vessel volume: 1.5 liters
Pearl loading: 2470g
Cellulose paste flow velocity: 700g/min
Peripheral speed: 13m/s
Container cooling water temperature: 8 DEG C
Treatment channel number: 2
(embodiment 51)
Comprise the production of the cellulose nano-fibrous resin combination of modification
With the solid composition cellulose nano-fibrous relative to 5 weight portion cationic be 15 weight portions cloudy from The ratio of the solid composition of sub-property additive adds the anionic property of 4500g anionic property additive A-1 form The dilution of additive (Gu composition: 1 weight %) produces, to 1765g, the modified cellulose Nanowire that example 3 obtains After the slurry (concentration: 0.85 weight %) of dimension 3, use Polytron homogenizer (model: PT3100, Kinematica AG) and Eurostar numeral agitator (IKA Werke GmbH Co.) combination stirring institute Obtaining mixture 10 minutes, to form the cluster of modified cellulose nanofiber, (it is by adding with anionic property Add agent to neutralize the cationic of height displacement and cellulose nano-fibrous obtain)；It is derived from comprising modified fibre The slurry of dimension element nanofiber.
By the moulding resin of 300g polypropylene powder resin form (H-700, Prime Polymer Co., Ltd.) It is 100 weight portion moulding resins with the solid composition cellulose nano-fibrous relative to 5 weight portion cationic Ratio add the slurry comprising modified cellulose nanofiber cluster to, stirring 10 minutes the most further To obtain the slurry of the resin combination comprising modified cellulose nanofiber.
With Nutsche filter (filter diameter: 185mm) and filter flask, use aspirator (model: WJ-20, final vacuum: 23.3hPa (20 DEG C), Sibata Scientific Technology, Ltd.) make aforementioned The slurry of the resin combination comprising modified cellulose nanofiber carries out filtration under diminished pressure (nylon cloth, 110 sieves Mesh) after, adding filter-press residues to water content is below 40 weight %, thus obtains and comprise modified cellulose Nanowire The wet cake of the resin combination of dimension.
[being dried of the resin combination comprising modified cellulose nanofiber]
The wet cake of the aforementioned resin combination comprising modified cellulose nanofiber is put into twin-screw squeeze Go out machine (screw diameter: 15mm, Technovel Corp.), be dried process subsequently.Squeezed by twin-screw The drying condition going out machine use is as follows.
<drying condition>
Screw diameter: 15mm
Screw rod rotary speed: 200rpm
L/D:45
Discharge rate: 300 to 400g/hr (as solid composition)
Design temperature: C1 (100 DEG C), C2 (100 DEG C), C3 (100 DEG C), C4 (90 DEG C), C5 (90 DEG C), C6(90℃)
[modified cellulose nanofiber in moulding resin dispersed]
Comprise the resin combination double screw extruder being dried of modified cellulose nanofiber melted and Mixing and use granulator (model: VC, Nakatani Kikai Co., Ltd.) granulating (size: about 1.5mm × 1.5mm), thus obtain the particle that wherein disperse modified is cellulose nano-fibrous.Melted and mixed Refining condition is as follows.
<melted/compounding conditions>
Screw diameter: 15mm
Screw rod rotary speed: 200rpm
Discharge rate: about 1000g/hr
Design temperature: C1-C6 (200 DEG C), H/D (200 DEG C)
When mode as identical in embodiment 41 measures the gained that wherein disperse modified is cellulose nano-fibrous The film dispersiveness of grain and Izod impact values (kJ/m2) time, film dispersiveness is evaluated as zero and Chalpy impact Value is 3.73kJ/m2。
(embodiment 52)
(comprising the measurement of the full light transmission rate of the film of modified cellulose nanofiber)
Measure film cellulose nano-fibrous for the wherein disperse modified of dispersiveness evaluation in embodiment 41 Full light transmission rate (NHD2000 nephelometer, measuring method 3, light source: D65, Nippon Denshoku Industries Co.,Ltd.).Measure in 4 positions of film, and when its mean value is used as to measure During value, measuring full light transmission rate is 90.8 (t=0.1mm).
(embodiment 53 to 62 and comparative example 8 to 11)
Mode as identical in embodiment 52 measures the complete of the film of embodiment 42 to 51 and comparative example 4 to 7 making Light transmission rate, and each result is shown in Table 5.In comparative example 8 to 10, due to cellulose nanometer in film Fibril aggregation, so there is sizable change in the value for the full light transmission rate of each measurement position, and Mean value can not be calculated.
[table 5]
Industrial applicability
The modified cellulose nanofiber of the present invention is preferably used as the hardening agent of moulding resin.Owing to comprising Molding resin composition or the formed body of modified cellulose nanofiber have high mechanical properties, so it can For such as, wherein use the string (cellulose nano-fibrous) of conventional micro-fibrillation formed body and Comprise the field of the resin-formed body of the string of micro-fibrillation, and need more high mechanical properties (example Such as bending strength) field.Such as, comprise modified cellulose nanofiber molding resin composition or Formed body be effectively used for the conveying arrangements such as such as automobile, train, boats and ships or aircraft internals, External member and structural elements, the such as housing of electric product, the structure such as PC, TV or phone Material and intraware, construction material, stationery material, the housing of the office device such as such as OA device, Sports entertainment article and structural material.

Claims (8)

1. a modified cellulose nanofiber, it is by with fine with cationic in anionic property additive The cation group of dimension element nanofiber obtains, and wherein said cationic is cellulose nano-fibrous to be had The diameter mean value of 4nm to 800nm, the HLB value of described anionic property additive is 1 to 15.
Modified cellulose nanofiber the most according to claim 1, wherein said anionic property adds The anionic degree of agent is more than 20mgKOH/g.
Modified cellulose nanofiber the most according to claim 1, wherein said anionic property adds Agent is anionic property styrene resin, anionic property (methyl) acrylic resin, anionic property polyolefin At least one type of resin, anionic property polyester resin, rosin class and alkenyl succinate acids.
4. a resin combination, it comprises modified cellulose nanofiber according to claim 1 And moulding resin.
5. a formed body, it obtains by being molded resin combination according to claim 4.
6. a production method for modified cellulose nanofiber, comprising: come with anionic property additive Neutralize the cation group that cationic is cellulose nano-fibrous, wherein said cationic cellulose nanometer Fiber has the diameter mean value of 4nm to 800nm, the HLB value of described anionic property additive be 1 to 15。
The production method of modified cellulose nanofiber the most according to claim 6, wherein said the moon The anionic degree of ionic additive is more than 20mgKOH/g.
The production method of modified cellulose nanofiber the most according to claim 6, wherein said the moon Ionic additive be anionic property styrene resin, anionic property (methyl) acrylic resin, cloudy from Sub-property vistanex, anionic property polyester resin, rosin class and at least one class of alkenyl succinate acids Type.
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US20130345341A1 (en) 2013-12-26
JP5150792B2 (en) 2013-02-27
CN103476802A (en) 2013-12-25
EP2684898B1 (en) 2020-05-20
WO2012124652A1 (en) 2012-09-20
US9074077B2 (en) 2015-07-07

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